1-amino-2-aryloxy-4-sulfonamidoanthraquinones



United States Patent 3,324,150 l-AMINO-2-ARYLOXY-4-SULFONAMIDO- ANTHRAQUINONES James M. Straley and Ralph R. Giles, Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N .Y.,

a corporation of New Jersey No Drawing. Filed June 28, 1965, Ser. No. 467,740 The portion of the term of the patent subsequent to Jan. 8, 1980, has been disclaimed 8 Claims. (Cl. 260-373) This application is a continuation-in-part of our now abandoned US. patent application Ser. No. 135,148 filed Aug. 31, 1961.

This invention relates to new anthraquinone compounds and their application to the art of dyeing or coloring.

The dyeing of polyester textile materials, such as polyethylene terephthalate, has presented difiiculties. While it is known that the familiar disperse dyes, that is, waterinsoluble dyes, employed for the coloration of cellulose acetate frequently possess aifinity for polyester textile materials such as polyethylene terephthalate, by far the majority of the known disperse dyes for cellulose acetate exhibit poor fastness to light when applied to polyester textile materials. The new water-insoluble anthraquinone compounds of our invention possess good afiinity for polyester textile materials and give red dyeings thereon having good fastness properties, including good fastness to light. Additionally, they have good afiinity for cellulose acetate, for example, and yield dyeings of high quality thereon.

Polyester fabrics are usually heat set, after dyeing, at temperatures which often reach 375 F. to 400 F. If the dye is not fast to sublimation, it will be removed in part, at least, from the goods during this operation. Some dyes, otherwise suitable for dyeing polyester fabrics, are unsuitable because they are not fast to sublimation. The new anthraquinone compounds of our invention yield dyeings on the textile materials indicated herein which have excellent fastness to sublimation.

It is an object of our invention to provide new anthraquinone compounds. Another object is to provide a satisfactory process for the preparation of our new anthraquinone compounds. A further object is to provide dyed polyester textile materials which have good fastness properties. Another object is to provide dyed cellulose alkyl carboxylic acid ester textile materials which have good fastness properties. A particular object is to provide dyed polyethylene terephthalate textile materials which have good fastness properties. A further particular object is to provide dyed cellulose acetate textile materials which have good fastness properties.

We have discovered that the anthraquinone compounds having the formula:

NHr

wherein R represents a member selected from the group consisting of a monocyclic carbocyclic aryl nucleus of the benzene series devoid of a Water-solubilizing group such as sulfo and carboxyl, e.g. phenyl and the substituted phenyl groups given in the table and example below; and R represents a member selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 3 to 6 carbon atoms, the B- bromoethyl groups and the cyclohexyl group, are valuable dyes for coloring polyester and cellulose alkyl carboxylic acid ester, having 2 to 4 carbon atoms in the acid groups thereof, textile materials. These dye compounds, when applied to the aforesaid textile materials, have good affinity therefor and give red dyeings of high quality. In general, the dyeings obtained have good to excellent fastness to light, gas, washing, sublimation and crocking, and the compounds respond well to other tests for textile dyes such as described in the A.A.T.C.C. Technical Manual, 1964 edition.

As indicated below, the substituents attached to R serve primarily as auxochrome groups to control the color of the compounds and yield compounds particularly adapted :10 use as textile dyes satisfying the mentioned tests for yes.

It has been found that representative compounds of the above formula such as those of Examples 3 and 5 below possess substantially better affinity for cellulose ester textile fibers such as Estron cellulose acetate fibers than do similar compounds such as described in US. Patent 1,948,183 and in British Patents 790,952 and 363,027, e.g., 1-amin0-2-methoxy-4-methylsulfonamido anthraquinone, 1 amino 2 sulfo 4 methylsulfonamido anthraquinone, 1-amino-2-sulfo-4-butylsulfonamido anthraquinone and 1,4-diamino-2-phenoxy-3-sulfo anthraquinone.

It has further been found that contrary to the statement of the Pizzarello et al. US. Patent 2,773,071, Cellulose acetate dyes are known which are derived from 1-amino 2-halo-4-hydroxy anthraquinone or 1,4-diamino-2-haloanthraquinone by replacing the halogen atom with an alkoxy group. These dyes generally have poor gas fading properties and do not have very good aifinity for cellulose acetate. Colour Index, vol. I, page 1692, CI. 62015, vol. III, page 3501, lists 1,4 diamino-2-methoxyanthraquinone as Disperse Red 11 and 1-amino-2-methoxy-4-hydroxyanthraquinone is listed as Disperse Red 4 by Colour Index, vol. I, page 1688, CI. 60755, vol. III, page 3492 and it is there stated that both dyes build-up well on acetate, which is another way of saying that they have good affinity. Moreover, a representative dye of Example 5 of US. 2,773,071 does not exhibit substantially better affinty on cellulose acetate fibers than do the above dyes, CI. 62015 and CI. 60755.

More particularly, it has been found that the dyes of the above general formula such as the dye of Example 5, l-amino 2 (4-fi-hydroxyethoxyphenoxy)-4-methylsulfonamidoanthraquinone, when used for dyeing polyester fabrics such as Dacron polyester fabric, in the presence of metal salts such as copper salts, have much better stability in the presence of the metal salt than do dyes of US. Patent 2,773,071 such as l-amino-Z-(B-hydroxyethoxyphenoxy)-4-hydroxyanthraquinone, and than do the dyes of US. Patent 3,072,683 such as 1-amino-2- phenoxyethoxy-4-methylsulfonamido anthraquinone. Accordingly, the good ailinity and stability to metal salts of the compounds of the invention are most unobvious from the mentioned properties of the compounds of US. 2,773,071 containing the radical OC H OC H OH and the compounds of US. 3,072,683 containing the radical -OC H OC H both of which radicals are present in the compounds of the present invention.

Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, n-amyl, isoamyl, n-hexyl and isohexyl are illustrative of the alkyl groups represented by R ,8- methoxyethyl, B-ethoxyethyl, ,B-n-propoxyethyl and B-nbutoxyethyl are illustrative of the alkoxyalkyl groups represented by R Phenyl, alkylphenyl, alkoxyphenyl, nitrophenyl, chlorophenyl, brornophenyl, alkacylphenyl, carbalkoxyphenyl, N-alkylaminophenyl and N-hydroxyalkylaminophenyl are illustrative of the monocyclic aryl nuclei of the benzene series represented by R.

By cellulose alkyl carboxylic acid esters having two to four carbon atoms in the acid groups thereof, we-mean to include, for example, both hydrolyzed and unhydrolyzed cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate-propionate and cellulose acetate-butyrate.

The polyester textile materials that can be dyed with the new anthraquinone compounds of our invention include polyethylene terephthalate textile materials obtained for example as described in US. Patent 2,465,319 patented March 22, 1949, or other polyester textile materials formed from analogous fiber-forming linear polyesters, such as polyesters derived from p,p-diphenylsulfonedicarboxylic acid and various aliphatic acids and glycols as described in US. Patent 2,744,088 patented May 1, 1956 and polyesters derived from various acids, such as terephthalic acid and 1,4-cyclohexanedimethanol (1,4-dimethylolcyclohexane) as described in Kibler, Bell and Smith US. Patent 2,901,466.

The polyethylene terephthalate fibers sold on the market under the E. I. du Pont de Nemours and Company trademark Dacron and the polyester fibers sold on the market under the Eastman Kodak Company trademarks Kodel are illustrative of the polyester textile materials that can be dyed with the new anthraquinone compounds of our invention. These fibers are more particularly described in US. Patents 2,454,319 and 2,901,466, respectively. The polyester textile materials specifically referred to hereinbefore are linear polyesters having a melting point of at least 200 C. Polyesters having a lower melting point than 200 C. can also be dyed or colored with the new anthraquinone compounds of our invention.

The new anthraquinone compounds of our invention can be prepared in several ways:

(a) 1amino-2,4-dibromoanthraquinone is reacted with a sulfonamide compound having the formula R SO NH to replace the bromine atom in the 4-position with a group, following which the bromine atom in the 2-position is replaced by a OR group by treatment with a phenol or its salt.

(b) 1 amino 4 bromoanthraquinone-Z-sulfonic acid (bromamine acid) or its alkali metal salts is reacted with a sulfonamide compound having the formula R SO NH to replace the bromine atom with a group, following which the sulfonic acid group in the 2-position is replaced by a OR group by treatment with a phenol or its salt.

(c) The compounds of our invention can also be prepared by reacting a 1,4-diaminoanthraquinone compound containing a OR group in the 2-position with a sulfonyl halide having the formula R SO X.

R and R have the meaning previously assigned to them, while X represents a chlorine or bromine atom.

Polyester textile materials can be dyed with the anthraquinone compounds of the invention by known methods for dyeing polyester textile materials. The methods disclosed in US. Patents 2,757,604 and 2,880,050, for example, can be used. Cellulose alkyl carboxylic acid esters having 2 to 4 carbon atoms in the acid groups thereof textile materials likewise can be dyed with the anthraquinone compounds of the invention by known methods for dyeing such materials.

The following examples illustrate the anthraquinone compounds of the invention and their preparation.

Example 1 Eight grams of potassium hydroxide were dissolved in 30 grams of phenol at 150 C. Two grams of 1-amino-2- bromo 4 methylsulfonamidoanthraquinone were added and the temperature of the reaction mixture was held at about C. for 2 hours. The reaction mixture was then drowned in 200 ccs. of water containing a small amount of potassium hydroxide, and the resulting mixture was cooled. 1-amino2-phenoxy4-methylsulfonamidoanthraquinone precipitated and was recovered by filtration. It was washed with water until neutral and then dried at 60 C. It dyes polyester textile materials, such as Dacron and Kodel polyester fibers, bright red shades. A carrier, such as Dacronyx, is used in the polyester dyeing operation.

Example 2 A mixture of 5 grams of 1,4diamino2-phenoxyanthraquinone in 50 ccs. of trichlorobenzene was heated to C. and 3.5 grams of cyclohexanesulfonyl chloride were added and the temperature held at 180 C. until hydrogen chloride ceased to evolve. The reaction mixture was then cooled-to 65 C. and diluted with an equal volume of hexane. The reaction mixture was chilled to precipitate the reaction product which was recovered by filtration, washed with haxane and dried. I-arnino-2-phenoxy-4- cyclohexylsulfonamidoanthraquinone was thus obtained. It dyes polyester textile materials, such as Dacron and Kodel polyester fibers, bright red shades.

Example 3 Example 1 was repeated using 30 grams of hydroquinone mono-n-butyl ether instead of phenol. The dye compound obtained, 1amino-2-(4-n-butoxyphenoxy)-4-methylsulfonamidoanthraquinone, dyes polyester textile materials, such as Dacron and Kodel polyester fibers, bright red shades.

Example 4 methyl alcohol and 25 ccs. of hexane and finally with hexane alone. The partially purified reaction product was resulurried in hot hexane, filtered and dried at 60 C. l-amino-Z-(4-n-butoxyphenoxy) 4 methylsulfonamidoanthraquinone was thus obtained. It dyes polyester textile materials, such as Dacron and Kodel polyester fibers, red shades.

Example 5 4.5 grams of 1-amino-2-bromo4-methylsulfonamidoanthraquinone, 2.25 grams of potassium hydroxide, 9 grams of p-B-hydroxyethoxyphenol and 100 ccs. of ethyleneglycol monomethyl ether were refluxed together for 2 hours, cooled to 80 C. and drowned in 200 ccs. of water. The resulting mixture was chilled to 0 C., filtered and the precipitate which collected on the filter was washed with water until the filtrate was practically colorless. 1- amino-2-(4-B-hydroxyethoxypheuoxy) 4 methylsulfonamidoanthraquinone was thus obtained and was dried in a vacuum. It dyes polyester textile materials, such as Dacron and Kodel polyester fibers, red shades. It also dyes cellulose acetate red shades. The cellulose acetate dye- .ings are distinguished by their high degree of fastness to light and to gas fumes.

Example 6 Dacron and Kodel polyester fibers, bright red shades.

Example 7 Example 5 was repeated using 12 grams of 3-hydroxydiphenylamine in place of p-fi-hydroxyethoxyphenol. The dye compound obtained has the formula:

0 N SOzCH3 It dyes polyester textile materials, such as Dacron and Kodel polyester fibers, bright red shades.

Example 8 Example 2 was repeated using 4.4 grams of S-bromoethanesulfonyl chloride in place of cyclohexanesulfonyl chloride. 1-amino-2-phen0xy-4-,8-bromoethylsu1f0namidoanthraquinone Was obtained. It dyes polyester textile materials, such as Dacron and Kodel polyester fibers, bright red shades.

Example 9 Example 2 was repeated using 3.5 grams of n-hexanesulfonyl chloride in place of cyclohexanesulfonyl chloride. The dye compound obtained, 1-amin0-2-phen0xy-4- n-hexylsulfonamidoanthraquinone, dyes polyester textile materials, such as Dacron and Kodel polyester fibers, bright red shades.

Following the procedures described hereinbefore, the anthraquinone dye compounds of our invention indicated hereinafter are readily prepared.

0-0 0 H3 CH3 4) CH3 O-owmh OH3 0 04 0 C 2CH2O CHac a O 0 Ha CHa Q-o CH3 411120113 0-0 01120113 CHrCH3 H $01119 (n) 3 -N(CHa)2 -0n rlrnozrnon I No, --0H0 OH3 0-0 0 0 02m CH3 O5Hn(n) Q CH2CH2OCHCHCH2CH3 C OC3H (n) -0H3 Oath -OH3 --0 OCH3 -0113 @ocornom OHa Go OCHzCHzCHs --CH:

Q Isobutyl Isoam 1 y Q Isohexyl 7 Example 10 Eight grams of potassium hydroxide were dissolved in 30 grams of phenol at 150 C. 4.1 grams of 1-amino-4- ethylsulfonamidoanthraquinone 2 sulfonic acid were added and the temperature of the reaction mixture was held at about 150 C. for 2 hours. The reaction mixture was then drowned in 200 ccs. of water containing a small amount of potassium hydroxide, and the resulting mixture was cooled. 1-amino-Z-phenoxy-4-ethylsulfonarnidoanthraquinone precipitated and was recovered by filtration. It was washed with water until neutral and then dried at 60 C. It dyes polyester textile materials, such as Dacron and Kodel polyester fibers, bright red shades.

As noted hereinbefore, the new anthraquinone compounds of our invention dye polyester and cellulose alkyl carboxylic acid ester, having 2 to 4 carbon atoms in the acid groups thereof, textile materials red shades having good to excellent fastness to light, gas, washing, sublimation and crocking. All the anthraquinone compounds set forth in the detailed examples and in the tabulation given hereinbefore yield red dyeings on the aforesaid textile materials which have the fastness properties just noted.

The preparation of various intermediate compounds that can be used in the preparation of the anthraquinone compounds of our invention is described hereinafter.

Example 11 .Preparation of B-ethoxyethanesulfonamide 1683 grams of 2-bromoethyl ethyl ether (BrCH CH OCH CH in 1250 cc. of 95% ethyl alcohol and 450 cc. of water were heated to reflux. A solution of 126 grams of Na SO in 450 cc. of water was added over a period of 1.5 hours. The reaction mixture was evaporated to dryness and the residue obtained was extracted twice with boiling ethyl alcohol and then dried at 65 C. 81 grams of the material thus obtained were treated with 108 grams of PCl an exothermic reaction taking place. The reaction mixture was then heated for 3 hours on a steam bath, cooled and 500 cc. of ice and water were added. The oil which separated was distilled, boiling at 68-77" C./0.7-1.4 mm. 55 grams of the fi-ethoxyethane sulfonyl chloride thus obtained were dissolved in 400 cc. of benzene, the resulting reaction mixture was cooled to C. and anhydrous NH was bubbled through it for 2 hours. The NH Cl formed as a byproduct was removed by filtration and then the benzene was removed by evaporation. p-ethoxyethanesulfonamide (CH CH OCH CH SO NH was thus obtained as a rather oily product. It was used without further treatment.

All, or nearly all, the sulfonamide compounds having the formula R SO NH wherein R has the meaning previously assigned to it, are known compounds. Any not specifically described can be prepared in accordance with the methods used to prepare the known like sulfonamide compounds.

Example 12 4.04 grams of 1-amino-4-bromoanthraquinone-2-sodium sulfonate, 1.25 grams of ethanesulfonamide, 1.84 grams of sodium acetate, 0.1 gram of copper sulfate crystals and 150 cc. of water were refluxed together until 1 cc. of the solution added to 10 cc. of 10% aqueous sodium hydroxide gave a clear violet solution. This required about 2.5 hours. The reaction mixture thus obtained was cooled, made acid with sulfuric acid and the reaction product formed was salted out with sodium chloride. The reaction product was recovered by filtration, washed free of acid with a cold 5% aqueous sodium chloride solution and dried. 3.78 grams of 1-arnino-4-ethylsulfonamidoanthraquinone-Z-sulfonic acid were obtained as a red solid.

8 Example 13 5.15 grams of 1-amino-4-bromoanthraquinone-2-sodium sulfonate, 0.1 gram of crystalline copper sulfate, 1.66 grams of potassium carbonate, 1.84 grams of [3- ethoxyethanesulfonamide and 150 cc. of water were refluxed together for 5.5 hours at which time tests indicated the absence of bromamine acid. 25 grams of potassium chloride were added to the reaction mixture, following which the reaction mixture was cooled to 10 C. while stirring. The reaction product which precipitated was recovered by filtration, washed with a cold 10% aqueous potassium chloride solution and dried at 110 C.

Example 14 5.15 grams of 1-amino-4-bromoanthraquinone-Z-sodium sulfonate, 0.1 gram of crystalline copper sulfate, 1.66 grams of potassium carbonate, 1.81 grams of n-pentanesulfonamide and 150 cc. of water were refluxed together for 5 hours, at which time 50 cc. of water were added to maintain complete solution. lRefluxing was continued until tests indicated the absence of bromamine acid. The reaction mixture was then cooled to about 10 C. and then filtered. The reaction product collected on the filter was washed well with a cold aqueous 5% potassium chloride solution and dried at 110 C.

Example 15 Example 14 was repeated using 1.76 grams of n-butanesulfonamide instead of n-pentanesulfonamide. The bromine atom in the 4-position is replaced by an n-butylsulfonamido group.

Example 16 51.5 grams of 1-amino-4-bromoanthraquinone-2-sulfonic acid, 16.6 grams of potassium carbonate, 11.4 grams of methanesulfonamide, 0.5 gram of CuSO -5 H 0 and 1500 cc. of water were refluxed together for 6 hours. 150 grams of sodium chloride and grams of potassium chloride were added and then the reaction mixture was cooled to 10 C. and filtered. The slightly sticky precipitate recovered on the filter was dissolved by warming in 750 cc. of water. 5 grams of activated charcoal Were added to the reaction mixture which was brought to the boil and then filtered. 75 grams of potassium chloride were added to the hot filtrate, which was cooled to about 10 C. and then filtered. The potassium salt of 1-amino-4-methylsulfonamidoanthraquinone-2-sulfonate was recovered on the filter, washed with water and dried at 100 C.

Example 17 A mixture of 3.81 grams of 1-amino--2,4-dibromoanthraquinone, 1.18 grams of potassium acetate, one crystal of copper acetate, 40 cos. of n-amyl alcohol and 1.75 grams of fl-ethoxyethanesulfonamide was refluxed, with stirring, for 4 hours. The reaction mixture was cooled, and the product which precipitated was recovered by filtration, washed with methyl alcohol and then with hot water. 1-amino-2-bromo-B-ethoxyethylsulfonamidoanthraquinone was obtained.

The new anthraquinone compounds of our invention can be used to color the polyester and the cellulose alkyl carboxylic acid ester textile materials mentioned hereinbefore by methods well known to those skilled in the art to which this invention is directed. They may be directly applied to the material undergoing coloration in the form of an aqueous suspension which can be prepared by grinding them to a paste in the presence of a sulfonated oil, soap, sodium lignin sulfonate, or other suitable dispersing agent and dispersing the resulting paste in water.

In the case of cellulose alkyl carboxylic acid ester textile materials direct dyeing operations can, with ad-' vantage, be conducted at temperatures of about 70 to C., but any suitable temperature can be used. Thus,

the textile material, such as cellulose acetate, for example, to be dyed or colored is ordinarily added to the dye bath at a temperature lower than that at which the main portion of the dying is to be effected, a temperature approximating 45 C. to 55 C., for example, following which the temperature is raised to that selected for carrying out the dyeing operation.

While the temperatures given in the dyeing procedure ust set forth apply primarily to cellulose alkyl carboxylic acid ester textile materials, with the modifications indicated hereinafter, this dyeing procedure also applies to the dyeing of polyester textile materials. As understood by those skilled in the dyeing art somewhat higher temperatures than those set forth in the preceding paragraph are ordinarily employed when polyester textile materials are being dyed. These latter materials are ordinarily dyed at the boil and usually an assistant, cmmonly known as a carrier is employed. The carriers have various active ingredients, such as chlorinated benzenes and o-phenylphenol, for example, in emulsion. Dacronyx is the trade name of an illustrative suitable carrier.

As is understood by those skilled in the dyeing art, the intensity of dyeing can be varied by varying the proportion of dye to material undergoing coloration. The amount of dye used can be, for example, /a to 3% (by weight) of that of the textile material, although lesser or greater amounts of dye can be used.

The following example illustrates one satisfactory way in which polyester textile materials can be dyed with the new anthraquinone compounds of our invention.

Example 18 0.3 gram of a 33.3% dispersion of l-amino-Z-phenoxy-4-methylsulfonamidoanthraquinone was added to 50 cc. of cold water and stirred until completely wet out. One cc. of a2% Igepon T solution was added and the dyebath was brought to a volume of 300 cc. with water. Three cc. of Dacronyx (a chlorinated benzene emulsion) were added and grams of a textile fabric made of Kodel polyester fibers were entered. The fabric was Worked 10 minutes without heat and then for 10 minutes at 80 C. The dyebath was then brought to the boil and held at the boil for one hour. Following this, the fabric was rinsed with water and dried. The fabric was dyed a beautiful red shade having excellent fastness to light, gas, washing, sublimation and crocking.

A similar result is obtained when the fabric is made of Dacron polyester fibers.

Other carriers, such as methyl salicylate, methyl terephthalate and o-phenylphenol, for example, can be used instead of the Dacronyx employed in Example 18.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim: 1. The anthraquinone compounds having the formula: El) NH2 o II 0 N-SO2R1 wherein R represents a member of the group consisting of phenyl, lower alkoxyphenyl, lower alkylphenyl, chloro- 10 phenyl, bromophenyl, lower N-alkylaminophenyl, anilinophenyl, hydroxyphenyl, lower hydroxyalkylaminophenyl, nitrophenyl, formylphenyl, lower carboalkoxyphenyl and lower alkacylphenyl, and R represents either alkyl of 1 to 6 carbon atoms, alkoxyalkyl of 3 to 6 carbon atoms, fl-bromoethyl or cyclohexyl.

2.. The anthraquinone compounds of claim 1 wherein R represents alkyl of 1 to 6 carbon atoms.

3. The anthraquinone compounds of claim 1 wherein R represents methyl.

4. The anthraquinone compound having the formula:

5. The anthraquinone compound having the formula:

6. The anthraquinone compound having the formula:

0 g-SMCH; 7. The anthraquinone compound having the formula:

i r 0 0oo112o112011 o N-SOzOH H 8. The anthraquinone compound having the formula:

El) NH References Cited UNITED STATES PATENTS 2,773,071 12/1956 Pizzarello et al 260-380 2,888,467 5/ 1959 Richter 260-3 80 3,072,683 1/1963 Straley et al. 260373 X 3,087,773 1/ 1963 Straley et a1 260-373 X FOREIGN PATENTS 790,952 2/ 1958 Great Britain.

LORRAINE A. WEINBERGER, Primary Examiner.

HAROLD WEGNER, Examiner. 

1. THE ANTHRAQUINONE COMPOUNDS HAVING THE FORMULA: 